EP3677611B1 - Composition de résine époxy thermodurcissable à basse température de durcissement et à bonne stabilité au stockage - Google Patents

Composition de résine époxy thermodurcissable à basse température de durcissement et à bonne stabilité au stockage Download PDF

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Publication number
EP3677611B1
EP3677611B1 EP19150161.8A EP19150161A EP3677611B1 EP 3677611 B1 EP3677611 B1 EP 3677611B1 EP 19150161 A EP19150161 A EP 19150161A EP 3677611 B1 EP3677611 B1 EP 3677611B1
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Prior art keywords
epoxy resin
resin composition
group
weight
thermosetting
Prior art date
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EP19150161.8A
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German (de)
English (en)
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EP3677611A1 (fr
Inventor
Noah Munzinger
Dominique Gallo
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Sika Technology AG
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Sika Technology AG
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Priority to EP19150161.8A priority Critical patent/EP3677611B1/fr
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP19824364.4A priority patent/EP3906271A1/fr
Priority to US17/287,067 priority patent/US11891507B2/en
Priority to JP2021527219A priority patent/JP7602458B2/ja
Priority to BR112021007419-8A priority patent/BR112021007419B1/pt
Priority to KR1020217012556A priority patent/KR102858553B1/ko
Priority to PCT/EP2019/086914 priority patent/WO2020141130A1/fr
Priority to CN201980082315.6A priority patent/CN113166375B/zh
Publication of EP3677611A1 publication Critical patent/EP3677611A1/fr
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    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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    • C08G59/46—Amides together with other curing agents
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C08L21/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin

Definitions

  • the invention relates to the field of heat-curing epoxy resin compositions, in particular for use as body-in-white adhesive.
  • Thermosetting epoxy resin compositions have been known for a long time. Efforts have been made for some time to eliminate or at least greatly reduce the major disadvantage of epoxy resin compositions, namely their brittleness, which when subjected to impact stress causes the cured epoxy resin composition to crack or be destroyed. This has already been attempted by adding toughness modifiers or chemically modifying epoxy resins.
  • accelerators can be used to ensure rapid curing.
  • Known categories of accelerators are, for example, latent imidazoles and amine-boron trifluoride complexes.
  • WO 2009/063043 A1 discloses a heat-curing epoxy resin composition with good storage stability for use as a shell construction adhesive comprising an epoxy resin, at least one hardener for epoxy resins, which is activated by elevated temperature, and a non-aromatic urea accelerator.
  • JP 2016130287 A discloses a microencapsulated hardener system for epoxy resins that leads to good crack resistance of the cured product.
  • WO 2016/159224 A1 shows a curable epoxy resin composition with good storage stability containing core-shell polymers and blocked isocyanate prepolymers as impact modifiers.
  • the object of the present invention is therefore to provide heat-curing epoxy resin compositions which, on the one hand, have good storage stability at room temperature and, on the other hand, have rapid curing at temperatures of 130.degree. C. to 140.degree.
  • This object could be achieved by a heat-curing epoxy resin composition according to claim 1.
  • This epoxy resin composition can be used particularly well as a one-component, heat-curing adhesive, in particular as a heat-curing, one-component body shell adhesive in vehicle construction.
  • molecular weight means the molar mass (in grams per mole) of a molecule.
  • average molecular weight is the number-average molecular weight M n of an oligomeric or polymeric mixture of molecules, which is usually determined by means of GPC against polystyrene as the standard.
  • primary amino group denotes an NH 2 group attached to an organic residue
  • secondary amino group denotes an NH group attached to two organic residues which also together form part of a ring can, is bound. Accordingly, an amine having a primary amino group is referred to as a "primary amine", one having a secondary amino group is similarly referred to as a “secondary amine” and one having a tertiary amino group is referred to as a "tertiary amine”.
  • room temperature A temperature of 23° C. is referred to as “room temperature” in the present document.
  • the epoxy resin A with an average of more than one epoxy group per molecule is preferably a liquid epoxy resin or a solid epoxy resin.
  • the term "solid epoxy resin” is well known to the epoxy specialist and is used in contrast to "liquid epoxy resins”.
  • the glass transition temperature of solid resins is above room temperature, ie they can be crushed into pourable powders at room temperature.
  • Preferred epoxy resins have the formula (II).
  • substituents R′ and R′′ independently of one another are either H or CH 3 .
  • the index s is >1.5, in particular from 2 to 12.
  • Such solid epoxy resins are commercially available, for example, from Dow or Huntsman or Hexion.
  • the index s is less than 1. s is preferably less than 0.2.
  • DGEBA diglycidyl ethers of bisphenol-A
  • Such liquid resins are available, for example, as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER TM 331 or DER TM 330 (Dow) or Epikote 828 (Hexion).
  • epoxy novolaks are also suitable as epoxy resin A.
  • Such epoxy resins are commercially available under the trade names EPN or ECN, such as Tactix® from Huntsman, or under the DEN TM product line from Dow Chemical.
  • the epoxy resin A is preferably a liquid epoxy resin of the formula (II).
  • the heat-curing epoxy resin composition contains both at least one liquid epoxy resin of the formula (II) with s ⁇ 1, in particular less than 0.2, and at least one solid epoxy resin of the formula (II) with s>1.5, in particular 2 until 12.
  • the proportion of epoxy resin A is preferably 10-60% by weight, in particular 30-50% by weight, based on the total weight of the epoxy resin composition.
  • epoxy resin A is an aforementioned solid epoxy resin.
  • composition according to the invention also contains, as hardener B , a dihydrazide selected from the group consisting of glutaric acid dihydrazide, adipic acid dihydrazide and pimelic acid dihydrazide. It is preferably adipic acid dihydrazide.
  • the ratio of the proportion of epoxide groups in epoxy resin A in mole/ proportion of dihydrazide in mole is preferably 3-5, in particular 3.5-4.5. This is advantageous in that high values for the mechanical properties of the cured composition, in particular for E modulus and tensile strength, are obtained in this range.
  • the dihydrazide has an average particle size D 50 of ⁇ 100 ⁇ m, ⁇ 50 ⁇ m, 0.5-50 ⁇ m, 1-50 ⁇ m, 1-40 ⁇ m, in particular 1-20 ⁇ m, preferably 2-20 ⁇ m, particularly preferably 2-15 ⁇ m , on.
  • mean particle size refers to the D 50 value of the cumulative volume distribution curve at which 50% by volume of the particles have a diameter smaller than the value.
  • the average particle size or the D 50 value is determined by laser diffractometry.
  • D 10 , D 50 , D 90 and D 98 denote those diameters at which 10% by volume, 50% by volume ("mean particle size"), 90% by volume and 98% by volume, respectively of the particles have a smaller diameter, determined by laser diffraction.
  • the heat-curing epoxy resin composition contains as little dicyandiamide as possible. If the epoxy resin composition contains dicyandiamide, the weight ratio of dihydrazide to dicyandiamide is ⁇ 0.5, ⁇ 0.75, ⁇ 1, ⁇ 2, ⁇ 5, in particular ⁇ 10, preferably ⁇ 50, particularly preferably ⁇ 100.
  • the amount of dicyandiamide is preferably less than 5% by weight, less than 3% by weight, less than 2% by weight, in particular less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.3% by weight, most preferably less than 0.1% by weight, based on the total weight of the epoxy resin composition.
  • the heat-curing epoxy resin composition particularly preferably contains no dicyandiamide.
  • compositions which contain dicyandiamide instead of the dihydrazides according to the invention do not cure at curing temperatures of 130-140.degree. This can be seen, for example, in Table 2 in the comparison of E1 and E2 with R4 - R8.
  • an "araliphatic radical” is understood to mean an aralkyl group, ie an alkyl group substituted by aryl groups (cf. Römpp, CD Römpp Chemie Lexikon, Version 1, Stuttgart/New York, Georg Thieme Verlag 1995 ).
  • R 1 is an n-valent aliphatic, cycloaliphatic or araliphatic radical and not an aromatic or heteroaromatic radical.
  • the accelerator C in particular does not have the formula (I').
  • R 3' is not H, R 3' is not an aromatic or heteroaromatic radical, ie the accelerator C in particular does not have the formula (I"). where Z 1 and Z 2 are H or any organic radical.
  • accelerators with aromatic radicals R 1 are not storage-stable, ie they increase the viscosity of heat-curing epoxy resin compositions within a short time to an extent that is no longer negligible for handling the composition.
  • R 1 is in particular a residue of an aliphatic, cycloaliphatic or araliphatic mono-, di-, tri- or tetraisocyanate of the formula (III) after removal of the n isocyanate groups.
  • This mono-, di-, tri- or tetra-isocyanate of the formula (III) is either a monomeric mono-, di-, tri- or tetra-isocyanate or a dimer or oligomer of one or more monomeric di- or triisocyanates, the dimer or oligomer being in particular biurets, Isocyanurates and uretdiones apply.
  • Suitable monomeric monoisocyanates are alkyl isocyanates, such as butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, decyl isocyanate and dodecyl isocyanate, as well as cyclohexyl isocyanate, methylcyclohexyl isocyanate and benzyl isocyanate.
  • Particularly suitable monomeric diisocyanates are 1,4-butane diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, dicyclohexylmethyl diisocyanate (H 12 MDI), m-tetramethylxylylene diisocyanate (TMXDI) and m-xylylene diisocyanate (XDI) and hydrogenated m-xylylene diisocyanate (HsXDI).
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TMDI trimethylhexamethylene diisocyanate
  • TMXDI m-tetramethylxylylene diisocyanate
  • XDI m-xy
  • dimers or oligomers are HDI biuret, HDI isocyanurate, IPDI biuret, IPDI isocyanurate, HDI diuretdione, IPDI isocyanurate,
  • dimers or oligomers are commercially available, for example, as Desmodur N-100 (Bayer), Luxate HDB 9000 (Lyondell), Desmodur N-3300 (Bayer), Desmodur N-3600 (Bayer), Luxate HT 2000 (Lyondell), Desmodur N- 3400 (Bayer), Luxate HD 100 (Lyondell), Desmodur Z 4470 (Bayer), Vestanat T 1890/100 (Hüls) or Luxate IT 1070 (Lyondell).
  • HDI, IPDI, HDI biuret and XDI, particularly preferably IPDI, after removal of the NCO groups are particularly preferred as R 1 .
  • R 2 and R 3 together can form a butylene, pentamethylene or hexamethylene group, preferably a pentamethylene group.
  • R 2 and R 3 particularly preferably each independently represent an alkyl group having 1 to 5 carbon atoms, in particular each independently represent a methyl, ethyl or propyl group, preferably each a methyl group.
  • R 1 represents H. This is preferred in the case where R 2 and R 3 each independently represent a methyl, ethyl or propyl group, preferably each a methyl group.
  • R 1 more preferably represents an n-valent aliphatic, cycloaliphatic or araliphatic radical.
  • R 1 ' on the one hand is in particular a diamine which is selected from the group consisting of 1,4-diaminobutane, hexamethylenediamine, isophoronediamine, trimethylhexamethylenediamine, 2,5- or 2,6-bis-(aminomethyl)-bicyclo[2.2.1 ] heptane, dicyclohexylmethyldiamine, m-tetramethylxylylenediamine and m-xylylenediamine, hydrogenated m-xylylenediamine, ethylenediamine, 1,3-propanediamine and 1,2-propanediamine after removal of the two amino groups.
  • a diamine which is selected from the group consisting of 1,4-diaminobutane, hexamethylenediamine, isophoronediamine, trimethylhexamethylenediamine, 2,5- or 2,6-bis-(aminomethyl)-bicyclo[2.2.1 ] heptane,
  • R 2 ' on the one hand is in particular a C 1 -C 10 -alkyl radical or an aralkyl radical having 7 to 20 carbon atoms, preferably a methyl, ethyl, propyl, butyl or pentyl group.
  • R 1' represents in particular an ethylene, propylene, butylene, methylethylene or 1,2-dimethylethylene group.
  • R 2' represents in particular an ethylene, propylene, butylene, methylethylene or 1,2-dimethylethylene group.
  • the two alkylene groups R 1' and R 2' together with the urea nitrogen atoms form a ring, in particular piperazine or 2,3,5,6-tetramethylpiperazine or homopiperazine (1,4-diazacycloheptane).
  • R 3' stands in particular for a monomeric monoisocyanate which is selected from the group consisting of butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, decyl isocyanate and dodecyl isocyanate, as well as cyclohexyl isocyanate, methylcyclohexyl isocyanate and benzyl isocyanate.
  • the accelerators C of the formula (Ia) are easily accessible synthetically from the reaction of an aliphatic, cycloaliphatic or araliphatic mono-, di-, tri- or tetraisocyanate of the formula (III) with a secondary amine of the formula (IV).
  • the accelerator C of the formula (Ia) is prepared from the reaction of a primary aliphatic, cycloaliphatic or araliphatic amine of the formula (V) and a compound of the formula (VI).
  • the accelerators C of the formula (Ib) are easily accessible synthetically from the reaction of an aliphatic, cycloaliphatic or araliphatic monoisocyanate of the formula (IIIa) with a secondary amine of the formula (IVa) or (IVb).
  • x' and y' each independently represent 1, 2, 3, 4 or 5 and the substituents Q 1' , Q 2' , Q 3' and Q 4' each independently represent H or a C 1 - to C 5 -alkyl group.
  • X′ and y′ are preferably 1 or 2, preferably 1 each, ie the secondary amine of the formula (IVb) is preferably piperazine or 2,3,5,6-tetramethylpiperazine or homopiperazine (1,4-diazacycloheptane), particularly preferably piperazine or 2,3,5,6-tetramethylpiperazine.
  • the secondary amines of the formula (IVa) can in turn be prepared particularly easily from the alkylation of primary amines of the formula R 1' [NH 2 ] n' .
  • Particularly preferred amines of the formula (IVa) are selected from the group consisting of N,N'-dimethyl-1,2-diaminocyclohexane, N,N'-dimethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, bis- Isopropylated IPDA (Jefflink-754 (Huntsman)), N,N'-diisobutyl-ethylenediamine and N-ethyl-N'-methyl-ethylenediamine.
  • the accelerator C has in particular a molecule of less than 1000 g/mol, in particular between 80 and 800 g/mol. If the molecular weight is larger, the acceleration effect is reduced and the amount required is significantly higher, which in turn can lead to poor mechanics.
  • the amount of accelerator C is advantageously 0.01-6.0% by weight, in particular 0.02-4.0% by weight, preferably 0.02-2.0% by weight, based on the weight of epoxy resin A.
  • the ratio of the proportion of accelerator C in grams per mole of epoxy groups in epoxy resin A is preferably 0.01-0.5 g/mol epoxy groups, in particular 0.05-0.3 g/mol epoxy groups, particularly preferably 0.075-0.2 g/mol epoxy groups, most preferably 0.08-0.15 g/mole of epoxide groups. This is advantageous in that in this range high storage stability is obtained with good mechanical values and good adhesion when cured at temperatures of 130-150.degree.
  • the one-component thermosetting epoxy resin composition preferably contains at least one toughener D.
  • the tougheners D can be solid or liquid.
  • the toughness improver D is selected from the group consisting of terminally blocked polyurethane polymers D1, liquid rubbers D2 and core-shell polymers D3 .
  • the toughener D is preferably selected from the group consisting of terminally blocked polyurethane polymers D1 and liquid rubbers D2 . It is particularly preferably a terminally blocked polyurethane polymer D1 .
  • the toughener D is a terminally blocked polyurethane polymer D1 .
  • phenols or bisphenols are particularly preferred as blocking groups.
  • Preferred examples of such phenols and bisphenols are in particular phenol, cresol, resorcinol, pyrocatechol, cardanol (3-pentadecenylphenol (from cashew nut shell oil)), nonylphenol, phenols reacted with styrene or dicyclopentadiene, bis-phenol A, bis-phenol -F and 2,2'-diallylbisphenol-A.
  • the terminally blocked polyurethane prepolymer is produced from an isocyanate-terminated, linear or branched polyurethane prepolymer with one or more isocyanate-reactive compounds. If several such isocyanate-reactive compounds are used, the reaction can take place sequentially or with a mixture of these compounds.
  • the reaction is preferably carried out in such a way that the one or more isocyanate-reactive compounds are stoichiometric or im stoichiometric Excess may be used to ensure that all NCO groups are reacted.
  • the polyurethane prepolymer with isocyanate end groups can be prepared from at least one diisocyanate or triisocyanate and from a polymer Q PM with terminal amino, thiol or hydroxyl groups and/or from an optionally substituted polyphenol Q PP .
  • Suitable diisocyanates are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular commercially available products such as methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), tolidine diisocyanate (TODI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 1,5-naphthalene diisocyanate (NDI), dicyclohexylmethyl diisocyanate (H 12 MDI), p-phenylene diisocyanate (PPDI), m-tetramethylxylylene diisocyanate (TMXDI), etc. and their dimers. HDI, IPDI, MDI or TDI are preferred.
  • Suitable triisocyanates are trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular the isocyanurates and biurets of the diisocyanates described in the previous paragraph. It is of course also possible to use suitable mixtures of di- or triisocyanates.
  • Particularly suitable polymers Q PM with terminal amino, thiol or hydroxyl groups are polymers Q PM with two or three terminal amino, thiol or hydroxyl groups.
  • the polymers Q PM advantageously have an equivalent weight of 300-6000, in particular 600-4000, preferably 700-2200 g/equivalent of NCO-reactive groups.
  • Preferred polymers Q PM are polyols with average molecular weights between 600 and 6000 daltons selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block polymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl-terminated butadiene-acrylonitrile copolymers and mixtures thereof.
  • Particularly preferred polymers Q PM are ⁇ , ⁇ -dihydroxypolyalkylene glycols with C.sub.2 -C.sub.6 -alkylene groups or with mixed C.sub.2 -C.sub.6 -alkylene groups which are terminated with amino, thiol or, preferably, hydroxyl groups.
  • Polypropylene glycols or polybutylene glycols are particularly preferred.
  • Hydroxyl-terminated polyoxybutylenes are also particularly preferred.
  • Bis-, tris- and tetraphenols are particularly suitable as polyphenol Q PP .
  • the type of substitution can be very diverse. In particular, this means substitution directly on the aromatic nucleus to which the phenolic OH group is attached.
  • phenols are understood to mean not only mononuclear aromatics, but also polynuclear or condensed aromatics or heteroaromatics which have the phenolic OH group directly on the aromatic or heteroaromatic.
  • the polyurethane prepolymer is produced from at least one diisocyanate or triisocyanate and from a polymer Q PM with terminal amino, thiol or hydroxyl groups.
  • the polyurethane prepolymer is prepared in a manner known to those skilled in the polyurethane art, in particular by using the diisocyanate or triisocyanate in a stoichiometric excess relative to the amino, thiol or hydroxyl groups of the polymer Q PM .
  • the polyurethane prepolymer with isocyanate end groups preferably has an elastic character. It preferably exhibits a glass transition temperature Tg of less than 0°C.
  • the toughness improver D can be a liquid rubber D2 .
  • This can be, for example, a carboxyl- or epoxide-terminated polymer.
  • this liquid rubber can be a carboxyl- or epoxide-terminated acrylonitrile/butadiene copolymer or a derivative thereof.
  • Such liquid rubbers are commercially available, for example, under the name Hypro/ Hyprox® CTBN and CTBNX and ETBN from Emerald Performance Materials.
  • Derivatives are, in particular, epoxide groups having elastomer-modified prepolymers, such as those sold commercially under the product line Polydis ® , in particular from the product line Polydis ® 36 .., by Struktol ® (Schill+Seilacher Group, Germany) or under the product line Albipox (Evonik, Germany). , suitable.
  • this liquid rubber can be a polyacrylate liquid rubber, which is completely miscible with liquid epoxy resins and only separates into microdroplets when the epoxy resin matrix hardens.
  • liquid polyacrylate rubbers are available from Dow, for example, under the designation 20208-XPA.
  • liquid rubbers can of course also be used, in particular mixtures of carboxyl- or epoxide-terminated acrylonitrile/butadiene copolymers or of derivatives thereof.
  • the toughness improver D can be a core-shell polymer D3 .
  • Core-shell polymers consist of an elastic core polymer and a rigid shell polymer.
  • Particularly suitable core-shell polymers consist of a core made of elastic acrylate or butadiene polymer, which is encased by a rigid shell of a rigid thermoplastic polymer. This core-shell structure is either formed spontaneously by the demixing of a block copolymer or is predetermined by the polymerisation process as a latex or suspension polymerisation with subsequent grafting.
  • Preferred core-shell polymers are so-called MBS polymers, which are commercially available under the trade name Clearstrength TM from Arkema, Paraloid TM from Dow or F-351 TM from Zeon.
  • the composition additionally contains at least one filler F.
  • This is preferably mica, talc, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicic acids (pyrogenic or precipitated), cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, hollow ceramic spheres, hollow glass spheres, organic hollow spheres, glass spheres, color pigments.
  • Fillers are particularly preferably selected from the group consisting of calcium carbonate, calcium oxide and pyrogenic silicic acids.
  • the total proportion of the entire filler F is advantageously 5-40% by weight, preferably 10-30% by weight, based on the total weight of the epoxy resin composition.
  • the composition can contain a physical or chemical blowing agent, as is available, for example, under the trade name Expancel TM from Akzo Nobel or Gelogen TM from Chemtura or under the trade name Luvopor® from Lehmann & Voss.
  • the proportion of blowing agent is advantageously 0.1-3% by weight, based on the total weight of the epoxy resin composition.
  • Hexanediol diglycidyl ether, cresyl glycidyl ether, p- tert -butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are particularly preferred.
  • the total proportion of the reactive diluent G bearing epoxide groups is advantageously 0.1-15% by weight, preferably 0.1-5% by weight, particularly preferably 0.1-2% by weight, particularly preferably 0.2-1% by weight, based on the total weight of the epoxy resin composition.
  • the composition can include other components, especially catalysts, stabilizers, especially heat and/or light stabilizers, thixotropic agents, plasticizers, solvents, mineral or organic fillers, blowing agents, dyes and pigments, anticorrosive agents, surfactants, defoamers and adhesion promoters.
  • catalysts especially catalysts, stabilizers, especially heat and/or light stabilizers, thixotropic agents, plasticizers, solvents, mineral or organic fillers, blowing agents, dyes and pigments, anticorrosive agents, surfactants, defoamers and adhesion promoters.
  • plasticizers are phenol-alkylsulfonic acid esters or benzenesulfonic acid-N-butylamide, such as are commercially available from Bayer as Mesamoll® or Dellatol BBS.
  • Particularly suitable stabilizers are optionally substituted phenols such as BHT or Wingstay® T (Elikem), sterically hindered amines or N-oxyl compounds such as TEMPO (Evonik).
  • the ratio of the proportion of accelerator C in grams per mole of epoxy groups in epoxy resin A is preferably 0.01-0.5 g/mol epoxy groups, in particular 0.05-0.3 g/mol epoxy groups, particularly preferably 0.075-0.2 g/mol epoxy groups, most preferably 0.08-0.15 g/mole of epoxide groups.
  • the ratio of the proportion of epoxide groups in epoxy resin A in mole/ proportion of dihydrazide in mole is preferably 3-5, in particular 3.5-4.5.
  • the preferred one-component epoxy resin composition contains more than 80% by weight, preferably more than 90% by weight, in particular more than 95% by weight, particularly preferably more than 98% by weight, most preferably more than 99 % by weight, based on the total weight of the epoxy resin composition, consists of the aforementioned components.
  • the epoxy resin composition according to the invention has a viscosity at 25° C. of 500-3000 Pa*s, in particular 1000 - 2500 Pa*s, preferably 1000 - 2000 Pa*s. This is advantageous in that it ensures good applicability.
  • the viscosity of the epoxy resin composition according to the invention decreases by less than 500%, by less than 300% less than 200%, less than 150%, less than 120%, less than 100%, less than 50%.
  • heat-curing epoxy resin compositions described are particularly suitable for use as one-component heat-curing adhesives, in particular as heat-curing one-component body shell adhesive in vehicle construction.
  • a one-component adhesive has a wide range of possible uses.
  • Such adhesives are required for bonding heat-stable materials.
  • Heat-stable materials are materials which are dimensionally stable at a curing temperature of 100-220° C., preferably 120-200° C., at least during the curing time.
  • these are metals and plastics such as ABS, polyamide, polyphenylene ether, composite materials such as SMC, unsaturated polyester GRP, epoxy or acrylate composites.
  • the application in which at least one material is a metal is preferred.
  • a particularly preferred use is the bonding of the same or different metals, especially in body shells in the automobile industry.
  • the preferred metals are above all steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel, bonazine-coated steel, and subsequently phosphated steel, and also aluminum, in particular in the variants typically found in automobile construction.
  • such an adhesive is first applied to the materials to be bonded at a temperature of between 10°C and 80°C, in particular between 10°C and 60°C, contacted and later cured at a temperature of typically 130-220°C, preferably 130-180°C, more preferably 130-150°C.
  • the substrate S2 consists of the same or a different material as the substrate S1.
  • the substrates S1 and/or S2 are, in particular, the metals and plastics mentioned above.
  • the composition is preferably heated to a temperature of 100-220° C., in particular 120-200° C., preferably between 130 and 150° C., particularly preferably between 130 and 140° C., the composition for 10 min - 6 h, 10 min - 2 h, 10 min - 60 min, 10 min - 30 min, 10 min - 20 min, particularly preferably 10 min - 15 min, left at the aforementioned temperature.
  • Such a method of bonding heat stable materials results in a bonded article.
  • Such an article is preferably a vehicle or part of a vehicle.
  • a further aspect of the present invention therefore relates to a bonded article obtained from the aforementioned method.
  • a composition according to the invention in addition to heat-curing Adhesives and sealants can be realized.
  • the compositions according to the invention are suitable not only for automobile construction but also for other areas of application. Special mention should be made of related applications in the construction of means of transport such as ships, trucks, buses or rail vehicles or in the construction of consumer goods such as washing machines.
  • the materials bonded by means of a composition according to the invention are used at temperatures between typically 120.degree. C. and -40.degree. C., preferably between 100.degree. C. and -40.degree. C., in particular between 80.degree. C. and -40.degree.
  • a particularly preferred use of the heat-curing epoxy resin composition according to the invention is its use as a heat-curing one-component body shell adhesive in vehicle construction or as a stiffening compound or as a foamable, heat-curing composition for reinforcement in cavities of structural components and reinforcement elements.
  • a further aspect of the present invention relates to a cured epoxy resin composition as is obtained by heating a thermosetting epoxy resin composition as previously described in detail.
  • the heating is typically carried out in an oven at a temperature of 100 - 220°C, preferably between 130 and 150°C, particularly preferably between 130 and 140°C, preferably for 10 min - 6 h, 10 min - 2 h, 10 min - 60 min, 10 min - 30 min, 10 min - 20 min, particularly preferably 10 min - 15 min, at the aforementioned temperature.
  • accelerators C according to the invention are suitable in combination with the curing agents B according to the invention as accelerators for heat-curing epoxy resin compositions at curing temperatures, in particular between 130 and 150°C.
  • compositions E1 and E2 which only contains dicyandiamide as a hardener, does not harden under the curing conditions for measuring the tensile shear strength at 140° C. for 10 minutes and are therefore not suitable for use with or without an accelerator.
  • a resin liquid Epoxy Liquid Resin, DER 331 (Bisphenol A Diglycidyl Ether), Dow A resin solid Epoxy solid resin, (bisphenol A diglycidyl ether based), Dow B1 Adipic acid dihydrazide, Technicure ADH-J (mean particle size D 50 of 2.4 ⁇ m), A&C Catalysts Inc. B2 Adipic acid dihydrazide, Technicure ADH (mean particle size D 50 of 15 ⁇ m), A&C Catalysts Inc.
  • the ratio of the proportion of epoxide groups in epoxy resin A in mole/ proportion of dihydrazide in mole is called “B index” in Table 1 and is given in [mole EP groups/mole dihydrazide].
  • C index The ratio of the proportion of accelerator C in grams per mole of epoxy groups in epoxy resin A is referred to as "C index" in Table 1 and is given in [g accelerator/mol EP groups].
  • TSF Tensile shear strength
  • Test sheets of steel Elo H420 (thickness 1.5 mm) that had been cleaned and oiled back with Anticorit PL 3802-39S were bonded to an adhesive surface of 25 x 10 mm with glass beads as spacers in a layer thickness of 0.3 mm with the adhesive and heated for 10 min at 140 °C oven temperature cured.
  • the tensile shear strength was determined on a tensile machine at a tensile speed of 10 mm/min in a triple determination in accordance with DIN EN 1465.
  • IP RT Impact peel strength
  • the specimens were made with the adhesive and steel DC04+ZE with the dimensions 90 x 20 x 0.8 mm.
  • the adhesive area was 20 x 30mm with a layer thickness of 0.3mm and glass beads as spacers.
  • the samples were cured for 10 min at 140°C oven temperature.
  • the impact peel strength was measured at 23° C. in triplicate on a Zwick 450 impact pendulum.
  • the mean force in N/mm under the measurement curve from 25% to 90% according to ISO11343 is given as the impact peel strength.
  • Viscosity measurements on the adhesives were carried out 1d after preparation on an Anton Paar MCR 101 rheometer using an oscillatory plate-plate geometry at a temperature of 25° C. with the following parameters: 5 Hz, 1 mm gap, plate-plate distance 25mm, 1% deformation. The measurement is shown in Table 2 under "Visco initially 25°C".
  • the viscosity measurement was repeated after storage at the specified temperature for a specified time in weeks, and the percentage increase in viscosity resulting after storage was determined.
  • the measured viscosity in Pa*s measured at a Temperature of 25°C after storage for 1 week at 50°C or 60°C is shown in Table 2 under “Visco 1W 50 25°C” or “Visco 1W 60 25°C”. The value in brackets shows the percentage increase in viscosity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Claims (12)

  1. Composition de résine époxy thermodurcissable comprenant
    a) au moins une résine époxy A comportant en moyenne plus d'un groupe époxyde par molécule ;
    b) au moins un agent de durcissement B pour des résines époxy, l'agent du durcissement B étant un dihydrazide choisi dans le groupe constitué par le dihydrazide d'acide glutarique, le dihydrazide d'acide adipique et le dihydrazide d'acide pimélique, de préférence le dihydrazide d'acide adipique ; et
    c) au moins un accélérateur C de formule (Ia) ou (Ib)
    Figure imgb0021
    R1 représentant H ou un radical n-valent aliphatique, cycloaliphatique ou araliphatique ;
    R2 et R3 représentant
    soit
    chacun indépendamment l'un de l'autre un groupe alkyle ou un groupe aralkyle ;
    soit
    ensemble un radical aliphatique divalent comportant 3 à 20 atomes de C, qui fait partie d'un cycle hétérocyclique, éventuellement substitué, comportant 5 à 8, préférablement 6, atomes de cycle ;
    R1' représentant un radical n'-valent aliphatique, cycloaliphatique ou araliphatique ;
    R2' représentant un groupe alkyle ou un groupe aralkyle ou un groupe alkylène ;
    R3' représentant, indépendamment l'un de l'autre, H ou un groupe alkyle ou un groupe aralkyle ; et
    n et n' représentant chacun une valeur de 1 à 4, en particulier 1 ou 2, et le dihydrazide présentant une taille moyenne de particule D50 de ≤ 100 µm, ≤ 50 µm, 0,5 à 50 µm, 1 à 50 µm, 1 à 40 µm, en particulier 1 à 20 µm, préférablement 2 à 20 µm, en particulier 2 à 15 µm, la taille moyenne de particule D50 étant déterminée par diffractométrie laser.
  2. Composition de résine époxy thermodurcissable selon la revendication 1, caractérisée en ce que R1 représente H et R2 et R3 représentent chacun un groupe méthyle, éthyle ou propyle, préférablement représentent chacun un groupe méthyle, et n = 1.
  3. Composition de résine époxy thermodurcissable selon la revendication 1, caractérisée en ce que R1 représente
    Figure imgb0022
     et R2 et R3 représentent chacun un groupe méthyle, éthyle ou propyle, préférablement représentent chacun un groupe méthyle, et n = 2.
  4. Composition de résine époxy thermodurcissable selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport proportion de groupes époxyde de la résine époxy A en moles/proportion de dihydrazide en moles est de 3 à 5, en particulier de 3,5 à 4,5.
  5. Composition de résine époxy thermodurcissable selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition de résine époxy thermodurcissable présente moins de 0,5 % en poids, préférablement moins de 0,3 % en poids, le plus préférablement moins de 0,1 % en poids, par rapport au poids total de la composition de résine époxy, de dicyandiamide.
  6. Composition de résine époxy thermodurcissable selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport de la proportion en accélérateur C en grammes par mole de groupes époxy de la résine époxy A est de 0,01 à 0,5 g/mole de groupes époxy, en particulier de 0,05 à 0,3 g/mole de groupes époxy, particulièrement préférablement de 0,075 à 0,2 g/mole de groupes époxy, le plus préférablement de 0,08 à 0,15 g/mole de groupes époxy.
  7. Composition de résine époxy thermodurcissable selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition de résine époxy thermodurcissable présente de plus au moins un agent d'amélioration de la robustesse D choisi dans le groupe constitué par des polymères de type polyuréthane bloqué en terminaison D1, des caoutchoucs liquides D2 et des polymères de type noyau-enveloppe D3, de préférence, il s'agit d'un polymère de type polyuréthane bloqué en terminaison D1.
  8. Composition de résine époxy thermodurcissable selon l'une quelconque des revendications précédentes, caractérisée en ce que la proportion de la résine époxy A est de 10 à 60 % en poids, en particulier de 30 à 50 % en poids, par rapport au poids total de la composition de résine époxy.
  9. Utilisation d'une composition de résine époxy thermodurcissable selon l'une quelconque des revendications 1 à 8 en tant qu'adhésif thermodurcissable monocomposant, en particulier en tant qu'adhésif de gros œuvre monocomposant thermodurcissable dans la construction de véhicules.
  10. Procédé de collage de substrats thermiquement stables comprenant les étapes
    i) application d'une composition de résine époxy thermodurcissable selon l'une quelconque des revendications 1 à 8 sur la surface d'un substrat thermiquement stable S1, en particulier d'un métal ;
    ii) mise en contact de la composition de résine époxy thermodurcissable appliquée avec la surface d'un autre substrat thermiquement stable S2, en particulier d'un métal ;
    iii) chauffage de la composition à une température de 100 à 220 °C, en particulier de 120 à 200 °C, préférablement comprise entre 130 et 150 °C, particulièrement préférablement entre 130 et 140 °C ;
    le substrat S2 étant constitué du même matériau que le substrat S1 ou étant constitué d'un matériau différent.
  11. Procédé selon la revendication 10, dans lequel dans l'étape iii) de chauffage de la composition à une température de 100 à 220 °C, en particulier de 120 à 200 °C, préférablement comprise entre 130 et 150 °C, particulièrement préférablement entre 130 et 140 °C, la composition est laissée à la température indiquée pendant 10 min à 6 h, 10 min à 2 h, 10 min à 60 min, 10 min à 30 min, 10 min à 20 min, particulièrement préférablement pendant 10 min à 15 min.
  12. Article collé obtenu par un procédé selon l'une quelconque des revendications 10 et 11.
EP19150161.8A 2019-01-03 2019-01-03 Composition de résine époxy thermodurcissable à basse température de durcissement et à bonne stabilité au stockage Active EP3677611B1 (fr)

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EP19150161.8A EP3677611B1 (fr) 2019-01-03 2019-01-03 Composition de résine époxy thermodurcissable à basse température de durcissement et à bonne stabilité au stockage
US17/287,067 US11891507B2 (en) 2019-01-03 2019-12-23 Thermosetting epoxy resin composition having low curing temperature and good storage stability
JP2021527219A JP7602458B2 (ja) 2019-01-03 2019-12-23 低い硬化温度及び良好な貯蔵安定性を有する熱硬化性エポキシ樹脂組成物
BR112021007419-8A BR112021007419B1 (pt) 2019-01-03 2019-12-23 Composição de resina epóxi termoendurecível, seu uso, processo para a ligação de substratos estáveis ao calor e artigo ligado por adesivo
EP19824364.4A EP3906271A1 (fr) 2019-01-03 2019-12-23 Composition de résine époxyde thermodurcissable présentant une faible température de durcissement et une bonne stabilité au stockage
KR1020217012556A KR102858553B1 (ko) 2019-01-03 2019-12-23 낮은 경화 온도 및 양호한 저장 안정성을 갖는 열경화성 에폭시 수지 조성물
PCT/EP2019/086914 WO2020141130A1 (fr) 2019-01-03 2019-12-23 Composition de résine époxyde thermodurcissable présentant une faible température de durcissement et une bonne stabilité au stockage
CN201980082315.6A CN113166375B (zh) 2019-01-03 2019-12-23 具有低固化温度和良好储存稳定性的热固化环氧树脂组合物

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JP7684039B2 (ja) * 2020-12-10 2025-05-27 パーカーアサヒ株式会社 エポキシ樹脂組成物
EP4067405A1 (fr) * 2021-04-01 2022-10-05 Sika Technology AG Composition de résine époxy durcissant à la chaleur adaptée aux procédés de préchauffage sans techniques supplémentaires d'assemblage des métaux
CN115798785B (zh) * 2022-12-12 2024-10-29 西北工业大学宁波研究院 一种用于汽车内饰功能器件的印刷电路银浆及其制备方法
DE102023106692A1 (de) 2023-03-17 2024-09-19 Thyssenkrupp Steel Europe Ag Bauteilgruppe mit strukturellen Verklebungen
EP4477685A1 (fr) * 2023-06-15 2024-12-18 Sika Technology AG Composition de résine époxy thermodurcissable appropriée pour une faible température de durcissement présentant une bonne stabilité au stockage
KR20250041838A (ko) 2023-09-19 2025-03-26 한국생산기술연구원 열안정성 듀얼 경화 조성물 및 이를 포함하는 듀얼 경화 접착제
EP4534580A1 (fr) * 2023-10-06 2025-04-09 Sika Technology AG Composition de résine époxy thermodurcissable appropriée pour une faible température de durcissement présentant une bonne résistance à la corrosion et un temps ouvert
EP4585632A1 (fr) * 2024-01-15 2025-07-16 Sika Technology AG Composition de résine époxy thermodurcissable appropriée pour une basse température de durcissement avec de bonnes capacités d'adhérence et de ténacité
EP4636033A1 (fr) * 2024-04-15 2025-10-22 Sika Technology AG Compositions de resine epoxy thermodurcissables a resistance au decollement amelioree
CN121319841A (zh) * 2025-12-16 2026-01-13 科建高分子材料（上海）股份有限公司 一种结构胶粘环氧组合物及其制备方法

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US20210355316A1 (en) 2021-11-18
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US11891507B2 (en) 2024-02-06
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